Process for the manufacture of polycondensation products containing phosphorus, the products and their use as flameproofing agents

ABSTRACT

The subject of the invention is a process for the manufacture of polycondensation products from hydroxymethylphosphonium compounds, characterized in that at least one anhydrous tetrakis-(hydroxymethyl)-phosphonium salt or tetrakis-(hydroxymethyl)-phosphonium hydroxide is condensed with itself in an anhydrous medium, optionally using an acid catalyst and optionally in the presence of at least one inert organic solvent, at 100° to 150° C, preferably 120° to 150° C, the condensation being continued until 0.5 to 1.5 mols of water have been eliminated per 1 mol of phosphonium compound employed, free hydroxyl groups are, if appropriate, at least partially etherified with at least one alkanol with 1 to 4 carbon atoms, and that the salt of the polycondensation products are, where relevant, converted into the corresponding hydroxides. 
     The polycondensation products are used for the flameproofing of organic fibre material, especially textiles. Appropriately, the procedure followed is that an aqueous preparation is applied to these materials which contains at least 1) a polycondensation product of the indicated type and 2) a polyfunctional compound, and that the material thus treated are dried and subjected to a heat treatment.

This is a divisional of application Ser. No. 399,576, filed on Sept. 21,1973, U.S. Pat. No. 3,907,898, which is a continuation of applicationSer. No. 164,054, filed on July 19, 1971, now abandoned.

The subject of the invention is a process for the manufacture ofpolycondensation products from hydroxymethylphosphonium compounds,characterized in that at least one anhydroustetrakis-(hydroxymethyl)-phosphonium salt ortetrakis-(hydroxymethyl)-phosphonium hydroxide is condensed with itselfin an anhydrous medium, optionally using an acid catalyst and optionallyin the presence of at least one inert organic solvent, at 100° to 150°C, preferably 120° to 150° C, the condensation being continued until 0.5to 1.5 mols of water have been eliminated per 1 mol of phosphoniumcompound employed, free hydroxyl groups are, if appropriate, at leastpartially etherified with at least one alkanol with 1 to 4 carbon atoms,and that the salts of the polycondensation products are, where relevant,converted into the corresponding hydroxides.

The condensation is preferably carried out at the reflux temperature ofthe solvent or solvent mixture employed. Suitable solvents are, aboveall, aromatic hydrocarbons, such as, for example, toluene, o- m- orp-xylene or a mixture thereof, or xylene-toluene, xylene-benzene orxylene-decahydronaphthalene mixtures. The self-condensation ispreferably carried out at 125° to 140° C, or especially at about 135° C.

At the same time it is however also possible to carry out thecondensation in the absence of an inert organic solvent, for example ifthe polycondensation product already prepared serves as the solvent, orif condensation is carried out in the melt.

Appropriately, the procedure followed is that firstly the water ofsolution is completely removed by distillation from thetetrakis-(hydroxymethyl)-phosphonium compound, which as a rule is in theform of an aqueous solution, and that then the self-condensation isinitiated. The process can be carried out continuously or stepwise.

Preferably, the self-condensation is continued until about 0.7 to 1.2mols, or in particular 0.8 to 1.2 mols, of water of condensation havebeen eliminated per 1 mol of phosphonium compound employed.

Amongst the tetrakis-(hydroxymethyl)-phosphonium salts used, thehalides, such as, for example, the bromide or especially the chloride,are preferred. Tetrakis-(hydroxymethyl)-phosphonium chloride ishereafter referred to as THPC.

Where tetrakis-(hydroxymethyl)-phosphonium hydroxide (THPOH) is used asthe starting product, it is appropriately manufactured beforehand from acorresponding salt, for examplr THPC, by neutralisation in aqueoussolution with a base, for example sodium hydroxide, and subsequentdehydration.

The polycondensation products thus obtained are higher-molecularcondensates which probably above all contain structural units of thefollowing constitution: ##STR1##

In addition, these polycondensation products probably also contain evenmore highly crosslinked products, which contain structural units of, forexample the following formula ##STR2##

The polycondensation products can furthermore also contain structuralunits of the following formulae: ##STR3## or, under certaincircumstances, also minor amounts of ##STR4##

Per molecule, the polycondensation products as a rule contain 2 to 200,preferably 2 to 20, or especially 2 to 10, structural units of theformulae (1) and/or (2).

The etherification, which may have to be carried out, of thepolycondensation product still containing free hydroxyl groups, is forexample effected with n-butanol, n-propanol, ethanol or especiallymethanol. Preferably, the process is carried out in an acid medium.

The acid catalysts which are optionally used conjointly in theself-condensation are preferably powerfully acid salts, (LEWIS acids)such as magnesium chloride, ferric chloride, zinc nitrate or borontrifluoride/diethyl ether. The conjoint use of these catalysts isparticularly advisable in the case of the self-condensation of THPOH,and where condensation is carried out below 120° C.

After completion of the self-condensation and, where relevant,etherification, the salts of the self-condensation products can also bewholly or partially converted into their corresponding hydroxides, andthis is as a rule effected by addition of strong bases, such as alkalihydroxides or alkaline earth hydroxides, for example sodium hydroxide,potassium hydroxide or calcium hydroxide, and also sodium carbonate. Theamount of base is appropriately so chosen that the pH-value of thereaction mixture is about 5 to 8.

At times, the end products possess an unpleasant odour, caused byvolatile, low-molecular trivalent phosphorus compounds, for examplephosphines such as trihydroxymethylphosphine. This odour can beeliminated by an oxidative after-treatment of the polycondensationproduct, for example by passing air or oxygen into the reaction mixture,or by addition of oxidising agents such as hydrogen peroxide orpotassium persulphate.

The polycondensation products are used for the flameproofing of organicfibre material, especially textiles. Appropriately, the procedurefollowed is that an aqueous preparation is applied to these materialswhich contains at least 1) a polycondensation product of the indicatedtype and 2) a polyfunctional compound, and that the materials thustreated are dried and subjected to a heat treatment.

The components 2) are preferably polyfunctional epoxides or above allpolyfunctional nitrogen compounds, Possible epoxides are above allepoxides with at least two epoxide groups, which are liquid at roomtemperature and are preferably derived from polyhydric phenols.Polyfunctional nitrogen compounds are, for example, polyalkylenepolyamines or especially aminoplast precursors or aminoplastprecondensates. The latter are preferred.

By aminoplast precursors there are understood nitrogen compounds whichcan be methylolated, and by aminoplast precondensates there areunderstood additon products of formaldehyde to nitrogen compounds whichcan be methylolated. The following may be mentioned as aminoplastprecursors or as nitrogen compounds which can be methylolated:

1,3,5-Aminortriazines such as N-substituted melamines, for exampleN-butylmelamine, N-trihalogenomethylmelamines, triazones and ammeline,guanamines, for example benzoguanamines or acetoguanamines, or alsodiguanamines.

Further possible compounds are: cyanamide, acrylamide, alkylureas orarylureas and alkylthioureas or arylthioureas, alkyleneureas oralkylenediureas, for example urea, thiourea, urones, triazones,ethyleneurea, propyleneurea, acetylenediurea or especially4,5-dihydroxyimidazolidone-2 and derivatives thereof, for example4,5-dihydroxyimidazolidone-2 which is substituted in the 4-position atthe hydroxyl group by the radical --CH₂ CH₂ CO--NH--CH₂ OH. The methylolcompounds of a urea, of an ethyleneurea or of melamine arepreferentially used. Valuable products are furnished in general byproducts which are methylolated as highly as possible, and especially bylow-methylolated products. Suitable aminoplast precondensates are bothpredominantly monomolecular aminoplasts and also more highlyprecondensed aminoplasts.

The ethers of these aminoplast precondensates can also be used togetherwith the reaction products. Advantageous examples are the ethers ofalkanols such as methanol, ethanol, n-propanol, isopropanol, n-butaol orpentanols. It is however desirable for these aminoplast precondensatesto be water-soluble, as is, for example,pentamethylolmelamine-dimethyl-ether.

The organic fibre materials to be provided with a flameproof finish are,for example, wood, paper, furs, hides or preferably textiles. Inparticular, fibre materials of polyamides, cellulose,cellulose-polyester or polyester are rendered flameproof, fabrics ofwool or polyester or mixed fabrics of polyester-cellulose, wherein theratio of the polyester part to the cellulose part is between 1:4 and2:1, being preferred. Thus, for example, so-called 20/80, 26/74, 50/50or 67/33 polyester-cellulose mixed fabrics can be used.

The cellulose or the cellulose component of the fibre material forexample originates from linen, cotton, rayon or staple viscose. Inaddition to polyester-cellulose fibre mixtures, it is also possible touse fibre mixtures of cellulose with natural or synthetic polyamides.Above all, fibre materials of wool can also be efficiently madeflameproof with the polycondensation products.

The aqueous preparations for the flameproofing of the organic fibrematerials as a rule contain 200 to 600 g/l, preferably 350 to 450 g/l,of the component (1) and 20 to 200 g/l, preferably 40 to 120 g/l, of thecomponents (2). The preparations mostly have an acid to a neutral orweakly alkaline pH-value.

The preparations for flameproofing can optionally contain yet furtheradditives. For example, the addition of 0.1 to 0.5 % of a high molecularpolyethylene glycol is advantageous for achieving a higher deposit ofsubstance on fabrics. Furthermore, the customary plasticisers, forexample an aqueous polyethylene emulsion, can be added to thepreparations.

To improve the mechanical strengths of the fibres, suitable copolymerscan also be added to the preparations, for example copolymers ofN-methylolacrylamide or cationic copolymers. For example, aqueousemulsions of copolymers of a) 0.25 to 10% of an alkaline earth salt ofan α,β-ethylenically unsaturated monocarboxylic acid, b) 0.25 to 30% ofa N-methylolamide or N-methylolamide-ether of an α,β-ethylenicallyunsaturated monocarboxylic acid or dicarboxylic acid and c) 99.5 to 60%of at least one other copolymerisable compound are advantageous. Thesecopolymers and their manufacture are known. The tear strength andabrasion resistance of the treated fibre material can be favourablyinfluenced by the conjoint use of such a copolymer.

If a polymer of the indicated type is further added to the preparation,the amounts added are advantageously small, for example 1 to 10%,relative to the amount of the polycondensation product. The same is trueof any plasticiser, where the appropriate amounts can again be 1 to 10%.

It is also possible to add curing catalysts such as, for example,ammonium chloride, ammonium dihydrogen orthophosphate, phosphoric acid,magnesium chloride or zinc nitrate, but this is in most cases notnecessary.

An addition of buffer substances, for example NaHCO₃, disodium phosphateand trisodium phosphate, or triethanolamine, can also be advantageous.

To improve the durability of the flameproof finishes and to achieve asoft handle, it can be advantageous to add halogenated paraffins, incombination with a polyvinyl halide compound, to the aqueouspreparations.

The preparations are now applied to the fibre materials, and this can beeffected in a manner which is in itself known. Preferably, piece goodsare used and are impregnated on a padder which is fed with thepreparation at room temperature.

The fibre material thus impregnated must now be dried, and this isappropriately done at temperatures of up to 100° C. Thereafter, it issubjected to a heat treatment at temperatures above 100° C, for example100° to 200° C, preferably 120° to 180° C, the duration of this can bethe shorter, the higher is the temperature. This period of heating is,for example, 30 seconds to 10 minutes.

It is furthermore also possible to use the so-called moist fixingprocess or wet fixing process.

A post-wash with an acid-binding agent, preferably with aqueous sodiumcarbonate solution, can be desirable in the case of a strongly acidreaction medium.

The percentages and parts in the examples which follow are percentagesby weight and parts by weight, respectively. The relationship of partsby volume to parts by weight is as of ml to g.

MANUFACTURING EXAMPLES EXAMPLE 1

1750 parts of a 78% strength aqueous solution of THPC (= 7.15 mol ofTHPC) and 1000 parts of m-xylene are heated to the boil, with rapidstirring, in a stirring flask of 4000 parts by volume capacity, equippedwith a reflux condenser, thermometer and water separator. The azeotropicremoval of the water from the aqueous THPC solution starts at a boilingpoint of 104° C. The calculated amount of water of 385 parts is obtainedwithin 3 hours, and the boiling point reaches 131° C.

A further 145 parts of water are now removed azeotropically byadditional treatment for a further 91/2 hours at 135° C, this waterhaving been produced by self-condensation of the dehydrated THPC, withsimultaneous slight elimination of HCl. This amount of water correspondsto about 1.1 mols of water per mol of THPC. Thereafter the mixture iscooled to 60° C and diluted with 1000 parts of methanol, whereupon thestringy-viscous condensation product dissolves. The m-xylene-methanolmixture is thereafter removed in vacuo at 60° to 70° C.

1127 parts of condensation product are obtained in the form of acolourless, slightly cloudy, highly viscous resin. The product contains18.6% of phosphorus (THPC = 16.3% P) and is soluble in water in anyproportion to give a clear solution. The viscosity at 25° is 2030poises.

The addition of an aqueous solution of sodium lauryl-sulphate to theaqueous solution of the condensation product causes precipitation,thereby confirming the higher-molecular cationic character of thecondensation product manufactured according to the invention.Water-insoluble condensation products cannot be obtained with ammonia.

EXAMPLE 2

The procedure described in Example 1 is followed, but after completionof the condensation reaction the reaction product is only cooled to 90°C and is dissolved by adding 800 parts of water. Thereafter the whole iscooled to room temperature, the aqueous solution is separated from thexylene phase, and the water is again removed in vacuo. In doing so, itmay be of advantage to leave a part of the water in the product (that isto say, for example to manufacture an 80% strength aqueous solution),which permits convenient handling.

1515 parts of a clear, slightly syrupy solution are thus obtained,containing 80% of condensation product. To increase the storagestability, the aqueous solution can be buffered to pH 6 - 7, for exampleby adding trisodium phosphate or triethanolamine.

EXAMPLE 3

78 parts of anhydrous THPC (previously azeotropically dehydrated inbenzene) are suspended in 200 parts of m-xylene in a stirring flask of500 parts by volume capacity, equipped with a reflux condenser,thermometer and water separator, and are heated to the boiling point of134° to 135° C. A total of 7.4 parts of water are obtaind byself-condensation over the course of 3 hours, and this amountcorresponds to exactly 1 mol of water per mol of THPC. After cooling to90° C, the resinous condensation product is dissolved by adding 47 partsof water. Thereafter the mixture is cooled to room temperature, thexylene phase is separated off and the aqueous solution is concentratedin vacuo at 50° to 60° C until an 80% strength syrupy, colourlessproduct is obtained. Yield: 87 parts (80% strength).

EXAMPLE 4

190.5 parts (1 mol) of crystalline anhydrous THPC (dehydrated inbenzene) are first introduced into a stirring vessel of 500 parts byvolume capacity, equipped with a thermometer, water separator and refluxcondenser with vacuum connection, and are warmed to 135° C internaltemperature, whilst stirring. The product is fused at 80° C.

As soon as the temperature of 135° C is reached, the apparatus is placedunder a vacuum of 20 to 30 mm Hg by applying the vacuum connection tothe top end of the reflux condenser. After a total of 3 hours' reactiontime at 135° C, the condensation is complete and 19 parts (about 1.05mols) of water have been collected in the water separator. After coolingto room temperature, a very stringy-viscous, colourless, clear resin isobtained, which is soluble in water or methanol.

EXAMPLE 5

200 parts of the condensation product as described in Example 4 aredissolved in 100 parts of methanol in a stirring vessel of 500 parts byvolume capacity, equipped with a thermometer and reflux condenser, andetherified for 30 minutes at the reflux temperature (62° C), whilststirring. The solution has a pH of approx. 1.

Thereafter the mixture is cooled to 40°-45° C and the excess methanol isremoved in vacuo. 210 parts of partially etherified polycondensationproduct are obtained, having a less high viscosity than the startingproduct and giving a clear solution in dimethylformamide at 25° C.

EXAMPLE 6

244 parts of 78% strength THPC (= 1 mol of pure substance), 3.81 partsof magnesium chloride as catalyst (=2% relative to pure THPC) and 160parts by volume of toluene are introduced into a stirring vessel of 500parts by volume capacity equipped with a thermometer, reflux condenserand water separator. The mixture is boiled under reflux, whilst stirringuntil 1 mol of water (18 parts by volume) has been eliminated; thisrequires about 10 to 12 hours.

Thereafter, the solvent is removed in a rotary evaporator under reducedpressure. The reaction product is left as cloudy, slightly coloured,viscous syrup, in practically 100% yield.

EXAMPLE 7

190.5 parts of THPOH (1.11 mols), manufactured from THPC byneutralisation with aqueous NaOH and subsequent dehydration, togetherwith 3.81 parts of MgCl₂ (2% relative to THPOH) in 160 parts by volumeof xylene are heated to the boil whilst stirring, until no further wateris eliminated. 13 parts by volume of water (0.72 mol) are separated offin this way.

After evaporation of the solvent, the polycondensation product is leftas a viscous syrup in 93% yield.

The polycondensation product is soluble in water.

EXAMPLE 8

238 parts of an 80% strength aqueous THPC solution and 200 parts ofm-xylene are dehydrated and condensed, analogously to Example 1, in astirring vessel of 500 parts by volume capacity equipped with athermometer and water separator. 73 parts of water are obtained.

The viscous condensation product which has been freed of xylene andmethanol is again diluted to 80% solids content with water and isneutralised to pH 7.5 with 49.5 parts of a 30% strength by weightaqueous sodium hydroxide solution. During the neutralisation, thetemperature is kept at 15° to 20° C by cooling. The resulting solutioncontains 63% of active substance, partly in the form of the hydroxideand partly in the form of the chloride.

EXAMPLE 9

73.5 parts of a 78% strength solution of THPC (= 300 mols) and 42 partsof 1,3-xylene are warmed to the boil, with rapid stirring, in anenamelled stirring kettle of 160 parts by volume capacity, equipped witha water separator and thermometer. The azeotropic removal of the waterstarts at a boiling point of 103° C. The calculated amount of water of16.2 parts is obtained within 31/2 hours; the boiling point reaches 131°C.

A further 5.1 parts of water, which have been produced, withsimultaneous slight elimination of HCl, by self-condensation of thedehydrated THPC, are now removed azeotropically by an additionaltreatment for a further 71/2 hours at 136° to 137° C. This amount ofwater corresponds to about 0.95 mol of water per mol of THPC. Thereafterthe mixture is cooled to 60° C, the stirrer is stopped, and thesupernatant xylene is siphoned off as far as possible. The residue isdissolved in 13.5 parts of water and simultaneously cooled to 15° C,whilst stirring. The mixture is adjusted to pH 6 by adding 13.5 parts of30% strength aqueous sodium hydroxide solution and is subsequentlydistilled in vacuo at 50° C until the distillate contains no furtherxylene. After cooling to 20° C, the product is filtered through a felt,using pressure, in order to isolate the sodium chloride which hasseparated out.

69 parts of a dark red, clear solution, containing 64.5% of activesubstance and 5.5% of sodium chloride, are obtained. The pH of thesolution is 6.

EXAMPLE 10

170 parts of the condensation product described in Example 1 and 54.2parts of 2,3-dibromopropanol are dissolved in 55 parts ofdimethylformamide, in a stirring vessel of 500 parts by volume capacity,equipped with a reflux condenser and thermometer, and the mixture isstirred for 1 hour at 100° to 105° C. Thereafter the dimethylformamideis distilled off in vacuo at 70° to 80° C.

The residue is dissolved in 400 parts of water and the solution is freedof the water and of unreacted amounts of 2,3-dibromopropanol in vacuo at90° to 95°.

209 parts of a yellow liquid of low viscosity are obtained, this beingthe partially 2,3-dibromopropanoletherified form of the condensationproduct from Example 1.

EXAMPLE 11

235 parts (1 mol) of tetrakis-hydroxymethylphosphonium bromide aresuspended in 500 ml of xylene. The mixture is heated to the boil untilno further water is eliminated; in total, about 12 ml (0.66 mol) ofwater are eliminated. The xylene is then evaporated under reducedpressure and the product is obtained as a yellow-brown, viscous oil,which is used without further purification.

USE EXAMPLES Example 12

400 parts of the condensation product described in Example 1 togetherwith 60 parts of trimethylolmelamine are made up into a solution of atotal of 1000 parts by volume. The pH is 4 to 5.

A strip of fabric of each of 100% polyester, 50:50 polyester-cotton and67:33 polyester-cotton is padded in this solution, dried at 80° to 90° Cand thermofixed for 41/2 minutes at 160° C. The fabrics are subsequentlywashed for 30 minutes, at 40° C, in a solution which per liter of watercontains 5 parts of an all-purpose detergent based on soap.

After this wash, the deposits of fixed flameproofing agent are found tobe as follows:

100% polyester fabric = 27.2% relative to original fabric weight.

50:50 polyester-cotton = 27.0% relative to original fabric weight.

67:33 polyester-cotton = 20.6% relative to original fabric weight.

All fabrics possess a very good flameproof character, which remainsmaintained unchanged even after 5-fold repetition of the wash describedabove,.

EXAMPLE 13

Example 12 is repeated, but with the condensation product obtainedaccording to Manufacturing Example 3.

After a 5-fold wash (compare Example 12) the deposits of fixedflameproofing agent are found to be as follows:

100% polyester fabric = 32.3% relative to original fabric weight.

50:50 polyester-cotton = 29.4% relative to original fabric weight.

67:33 polyester-cotton = 20.4% relative to original fabric weight.

All fabrics possess a very good flameproof character, which remainsmaintained unchanged even after a 15-fold wash (compare Example 12).

EXAMPLE 14

400 parts of the condensation product from Example 4 and 60 parts oftrimethylolmelamine are dissolved in 500 parts of water and made up to1000 parts by volume with more water.

A fabric of each of 100% polyester, 50:50 polyester-cotton and 67:33polyester-cotton is treated analogously to the description in Example12.

After a 5-fold wash, all fabrics still have a very good flameproofcharacter and possess the following deposits of flameproofing agent andaminoplast resin:

    ______________________________________                                        100% polyester fabric:  26.5%                                                 50:50 polyester fabric: 24.8%                                                 67:33 polyester fabric: 18.0%                                                 ______________________________________                                    

Instead of the condensation product of Example 4, the condensationproduct according to Example 6 or Example 7 can also be employed withequally good success.

EXAMPLE 15

2 different woollen fabrics, weighing 92 g/m² and 165 g/m², are paddedin the same application bath as described in Example 14, dried at 90° Cand thermofixed (or cured) for 5 minutes at 120° C. Both fabrics aresubsequently washed for 20 minutes at 40° C, in a washing liquor of thefollowing composition:

200 parts of sodium tetraborate, 600 parts by volume of an aliphaticpolyethylene glycol ether (nonionic), 200 parts by volume of sec. Naalkylsulphate (anionic) and 9200 parts by volume of water (deionised).

After drying, both fabrics have a very good flameproof character and apleasant handle.

Untreated woollen fabric already combusts completely and very vigorouslyafter brief contact with the flame.

EXAMPLE 16

400 parts of the condensation product described in Example 5 and 60parts of trimethylolmelamine are made up into a solution of a total of1000 parts by volume. The pH is 4 to 5.

A strip of fabric of 67:33 polyester-cotton is treated in this solution,in the manner described in Example 12, and is washed. The deposit offixed flameproofing agent is 19.3%. The fabric has very good flameproofcharacter and only shows moderate stiffening of the handle. Theflameproof character remains preserved unchanged even after 5-foldrepetition of the wash described in Example 12.

EXAMPLE 17

A strip of wool fabric weighing 165 g/m² is treated with the same liquoras that described in Example 16, in the same manner, and washed. Thedeposit of fixed flameproofing agent is 32.6%.

The fabric has a very good flameproof character and a pleasant handle.The flameproof effect remains preserved unchanged even after 5-foldrepetition of the wash described in Example 12.

EXAMPLE 18

600 parts of the 63% strength product described in Example 8 and 60parts of trimethylolmelamine are made up into a solution of a total of1000 parts by volume. The pH is 7.

A strip of fabric of each of 100% polyester and 50:50 polyester-cottonis treated as indicated in Example 12.

The deposits of fixed flameproofing agent approximately correspond tothose of Example 12.

The fabrics have a very good flameproof character, which remainspreserved even aftr 5-fold repetition of the wash described in Example12.

EXAMPLE 19

An undyed 50:50 or 67:33 polyester-cotton fabric is padded with a liquorwhich per liter contains 480 g of the product according to Example 10and 85 g of dimethylolmelamine (yielding 67 g/l of phosphorus and 35 g/lof nitrogen) and is dried at 80° to 100° C. Thereafter the material iscured for 5 minutes at 150° C.

The fabrics are afterwards washed for 5 minutes at 60° C in a detergentsolution which contains 4 g/l of sodium carbonate and 1 g/l of acondensation product of 1 mol of p-tert.-nonylphenol and 9 mols ofethylene oxide.

A further part of this fabric is now washed 20 times or 40 times for 45minutes in a domestic washing machine, at 40° C, in a solution which perliter of water contains 4 g of a domestic detergent (=SNC-19,8861-wash).

The individual pieces of fabric are then tested for their flameproofcharacter (vertical test DIN 53,906). The results of this test weresummarised in the table below.

    ______________________________________                                                       Polyester/Cotton                                                                50:50    67:33                                               Degree of Fixing 61%      62%                                                 Flameproof Character:                                                                          Tear length* in cm                                                                          untreated                                      ______________________________________                                        after post-wash after 20 SNV 198861 washes after 40 SNV 198861                                 10.5 8.5 9                                                                             8 9 9.5                                                                                 ##STR5##                                  ______________________________________                                         *The tear length corresponds to the burning penetration length.          

EXAMPLE 20

An undyed 50:50 or 67:33 polyester-cotton fabric is padded with a liquorwhich per liter contains 530 g of the product according to Example 9, 85g of dimethylolmelamine and 0.25 g of a condensation product of 1 mol ofp-tert.-nonylphenol and 9 mols of ethylene oxide. The liquor thuscontains 67 g/l of phosphorus and 35 g/l of nitrogen and the pH-value is5.9. The liquor uptake is 80%. Thereafter the fabric is dried at about80° C and the material cured for 5 minutes at 150° C.

A part of the fabric is washed for 5 minutes at 60° C in a solutionwhich per liter contains 5 ml of hydrogen peroxide (30% strength), 3 gof sodium hydroxide solution (30% strength), 2 g of waterglass and 0.25g of a condensation product of 1 mol of p-tert.-nonylphenol and 9 molsof ethylene oxide.

The individual pieces of fabric are then tested for their flameproofcharacter (vertical test DIN 53,900). The test results are summarised inthe table which follows.

    ______________________________________                                                      un-     Polyester/Cotton                                                      treated 50:50     67:33                                         Degree of Fixing                                                                              --        67%       67%                                        Flameproof Character:                                                                               Tear Length in cm                                      ______________________________________                                        before post-wash                                                                              burns     11.5      11.5                                      after post-wash burns     10.5      11                                        ______________________________________                                    

EXAMPLE 21

An undyed 50:50 or 67:33 polyester-cotton fabric is padded with a liquorwhich per liter contains 468 g of the product according to Example 11,85 g of dimethylolmelamine and 0.25 g of a condensation product of 1 molof p-tert.-nonylphenol and 9 mols of ethylene oxide. The liquor thuscontains 67 g/l of phosphorus and 35 g/l of nitrogen and the pH-value(adjusted with sodium hydroxide) is 5.5. The liquor uptake is 80%.Thereafter the fabric is dried at about 80° C and the material cured for5 minutes at 150° C.

The individual pieces of fabric are then tested for their flameproofcharacter (vertical test DIN 53,900). The test results are summarised inthe table which follows.

    ______________________________________                                                      un-     Polyester/Cotton                                                      treated 50:50     67:33                                         Deposit on Fabric                                                                             --        35.5%     35.5%                                     ______________________________________                                        Flameproof Character:                                                         Tear length in cm                                                                             burns     12        10.5                                      ______________________________________                                    

EXAMPLE 22

An undyed 50:50 or 67:33 polyester-cotton fabric is padded with theliquors of the table which follows and dried at 80° to 100° C, and thematerial is subsequently cured for 41/2 minutes at 160° C.

The fabrics are then post-washed for 5 minutes at 60° C in a bath whichper liter contains 4 g of sodium carbonate and 1 g of a condensationproduct of 1 mol of p-tert.-nonylphenol and 9 mols of ethylene oxide.

A part of these fabrics is subjected to 20, and in part also 40,SNV-198861 washes (compare Example 19).

The individual pieces of fabric are then tested for their flameproofcharacter (vertical test DIN 53,906). The results of this test are alsosummarised in the table which follows.

    __________________________________________________________________________                       un-  Treated with Liquor                                   Constituents       treated                                                                            A    B    C    D    E    F    G                       __________________________________________________________________________    Product according to Example 9                                                                 g/l    415  415  415  415  415  415  415                     Condensation product .sup.1)                                                                   g/l    0.25 0.25 0.25 0.25 0.25 0.25 0.25                    MgCl.sub.2 . CH.sub.2 O                                                                        g/l    50   50   50   50   50   50   50                      Dimethylolmelamine                                                                             g/l    85                       20                           Hexamethylolmelamine-penta-                                                   methyl-ether     g/l         220                                              Dimethylol-4-hydroxypropylene-                                                urea             g/l              440                                         Propyleneurea    g/l                   400                                    Methylated urone g/l                             400                          Melamine         g/l                             33   53                      pH of the liquor, adjusted                                                    with NaOH               5.5  5.5  5.5  5.5  5.5  5.5  5.5                     __________________________________________________________________________     Flameproof Character   Tear Length in cm                                     __________________________________________________________________________    50:50 Polyester/Cotton                                                        after post-wash    burns                                                                              8.5  10.5 10   9.5  12   8.5  9                       after 20 SNV-198861 washes                                                                            8    11   8.5  7.5  8    9    8                       after 40 SNV-198861 washes                                                                            10.5 --   --   --   9    10   8                       67:33 Polyester/Cotton                                                        after post-wash    burns                                                                              11   12   --   9.5  9.5  9    10.5                    after 20 SNV-198861 washes                                                                            9    11   --   9    9    9    8                       after 40 SNV-198861 washes                                                                            9.5  --   --   --   10   10   8                       __________________________________________________________________________     .sup.1) of 1 mol of p-tert.nonylphenol and 9 mols of ethylene oxide      

EXAMPLE 23

An undyed 50:50 or 67:33 polyester-cotton fabric is padded with theliquors of the table which follows and dried at 80° to 100° C, thematerial is subsequently cured for 41/2 minutes at 160° C.

The fabrics are then post-washed for 5 minutes at 60° C in a bath whichper liter contains 4 g of sodium carbonate and 1 g of a condensationproduct of 1 mol of p-tert.-nonylphenol and 9 mols of ethylene oxide.

The individual pieces of fabric are then tested for their flameproofcharacter (vertical test DIN 53,906). The results of this test are alsosummarised in the table which follows.

    __________________________________________________________________________                       un-  Treated with Liquor                                   Constituents       treated                                                                            H    I    J    K    L    M    N                       __________________________________________________________________________    Product according to Example 9                                                                 g/l    415  415  415  415  415  415  415                     Condensation product .sup.1)                                                                   g/l    0.25 0.25 0.25 0.25 0.25 0.25 0.25                    MgCl.sub.2. CH.sub.2 O                                                                         g/l    50   50   50   50   50   50   50                      5,5-Dimethyl-4-methoxypropylene-                                              urea             g/l    535                                                   Dimethylolhydroxypropyleneurea                                                                 g/l         440                                              Ethyleneurea     g/l              365                                         Acetylenediurea  g/l                   330                                    Hydroxyethylenetriazone                                                                        g/l                        340                               Urea             g/l                             150                          Dimethylolmelamine                                                                             g/l                                  20                      Cyanamide        g/l                                  50                      pH of the liquor adjusted with                                                NaOH             g/l    5.5  5.5  5.5  5.5  5.5  5.5  5.5                      Flameproof Character   Tear Length in cm                                     __________________________________________________________________________    50:50 Polyester/Cotton                                                                           burns                                                                              7.5  --   7.5  11   12   9    10.5                    67:33 Polyester/Cotton  11.5 9    9    9.5  --   12   --                      __________________________________________________________________________     .sup.1) of 1 mol of p-tert.-nonylphenol and 9 mols of ethylene oxide     

EXAMPLE 24

An undyed 50:50 or 67:33 polyester-cotton fabric is padded with theliquors of the table which follows, dried at 80° to 100° C and thematerial is subsequently cured for 41/2 minutes at 160° C.

The individual pieces of fabric are then tested for their flameproofcharacter (vertical test DIN 53,906). The results of this test are alsosummarised in the table which follows.

    __________________________________________________________________________                       un-  Treated with Liquor                                   Constituents       treated                                                                            0    P    Q    R    S    T                            __________________________________________________________________________    Product according to Example 9                                                                 g/l    415  415  415  415  415  415                          Condensation product .sup.1)                                                                   g/l    0.25 0.25 0.25 0.25 0.25 0.25                         MgCl.sub.2 . CH.sub.2 O                                                                        g/l    50   50   50   50   50   50                           Dimethylolethylene-                                                           carbonate        g/l    530                                                   Methylolacrylamide                                                                             g/l         504                                              Dimethylolacrylamide                                                                           g/l              327                                         Dimethylolmelamine                                                                             g/l                   20   20   20                           Ammeline         g/l                   42                                     Glyoxalmonourein g/l                        104                               Cyanamide        g/l                             50                           pH of the liquor adjusted with                                                NaOH                    5.5  5.5  5.5  5.5  5.5  5.5                          __________________________________________________________________________    Flameproof Character    Tear Length in cm                                     __________________________________________________________________________    50:50 Polyester/Cotton  11   10.5 10.5 10.5 10   10.5                         67:33 Polyester/Cotton  --   9    9    --   --   10.5                         __________________________________________________________________________     .sup.1) of 1 mol of p-tert.-nonylphenol and 9 mols of ethylene oxide     

EXAMPLE 25

A mercerised, bleached cotton fabric is padded with a liquor whichcontains 195 g/l of the product according to Example 9, 116 g/l ofdimethylolmelamine and 2 g of a condensation product of 1 mol ofp-tert.-nonylphenol and 9 mols of ethylene oxide (yielding 35 g/l ofphosphorus and 48 g/l of nitrogen);

The liquor uptake is 80%. Thereafter the fabric is dried at 80° C andthe material cured for 5 minutes at 150° C.

The fabric is then boiled for 5 minutes in a bath which per litercontains 4 g of sodium carbonate and 1 g of a condensation product of 1mol of p-tert.-nonylphenol and 9 mols of ethylene oxide, and isthereafter rinsed and dried.

A part of this fabric is now further subjected to 65 machine washesaccording to SNV 198861 at 95° C (compare Example 19).

The individual pieces of fabric are then tested for their flameproofcharacter (vertical test DIN 53,906). The results of this test aresummarised in the table which follows.

    ______________________________________                                        Deposit on Fabric after Post-wash                                                                         13.5%                                             Degree of Fixing            61%                                               ______________________________________                                        Flameproof Character       treated  untreated                                 after the post-wash:                                                                       burning time, sec.                                                                          0        burns                                                  Tear length, cm                                                                             8                                                  after 65 × SNV-198861                                                                washes:                                                                       Burning time, sec.                                                                          0        burns                                                  Tear length, cm                                                                             8                                                  ______________________________________                                         Handle:  A trace stiffer than the untreated fabric?                      

EXAMPLE 26

An undyed 50:50 polyester/linen fabric or a 67:33 polyester/regeneratedcellulose fabric is padded with a liquor which contains 590 g/l of theproduct according to Example 9, 85 g/l of dimethylolmelamine and 2 g ofa condensation product of 1 mol of p-tert.-nonylphenol and 9 mols ofethylene oxide (yielding 67 g/l of phosphorus and 35 g/l of nitrogen).

The liquor uptake is 80% and 100% respectively. Thereafter the fabric isdried at 80° C and the material cured for 41/2 minutes at 160° C.

The fabric is then boiled for 5 minutes in a bath which per litercontains 4 g of sodium carbonate and 0.25 g of a condensation of 1 molof p-tert.-nonylphenol and 9 mols of ethylene oxide, and is then rinsedand dried.

A part of this fabric is now further subjected to 5 machine washesaccording to SNV 198861 at 40° C (compare EXAMPLE 19).

The individual pieces of fabric are then tested for their flameproofcharacter (vertical test, DIN 53,906). The results of this test aresummarised in the table which follows.

    ______________________________________                                                     50:50, Polyester/                                                                        67:33, Polyester/                                                 Linen       Regenerated                                                       Cellulose                                                                            un-               un-                                                  treated                                                                              treated  treated  treated                                  ______________________________________                                        Deposit on fabric                                                             after post-wash                                                                             18.2%    --       22.8%  --                                     Degree of Fixing                                                                             67%     --       67%    --                                     Flameproof Character                                                          after post-wash                                                               burning time, sec.                                                                           0       burns    0      burns                                  Tear length, cm                                                                             10.5              9                                             after 5 × SNV 198861                                                    washes:                                                                       Burning time, sec.                                                                           0       burns    0      burns                                  Tear length, cm                                                                             10                9                                             ______________________________________                                    

EXAMPLE 27

A wool gabardine fabric is padded with a liquor which contains 590 g/lof the product according to Example 9, 85 g/l of dimethylolmelamine and1 g of a condensation product of 1 mol of p-tert.-nonylphenol and 9 molsof ethylene oxide (yielding 67 g/l of phosphorus and 35 g/l ofnitrogen).

The liquor uptake is 80%. Thereafter the fabric is dried at 80° C andthe material cured for 41/2 minutes at 160° C.

The fabric is then boiled for 5 minutes in a bath which per litercontains 4 g of sodium carbonate and 0.25 g of a condensation product of1 mol of p-tert.-nonylphenol and 9 mols of ethylene oxide, and isthereafter rinsed and dried.

A part of this fabric is now further subjected to 5, 10 and 40 machinewashes according to SNV 198861 at 40° C (compare Example 19).

The individual pieces of fabric are then tested for their flameproofcharacter (vertical test, DIN 53,906). The results of this test aresummarised in the table which follows.

    ______________________________________                                        Deposit on Fabric after post-wash                                                                  14%                                                      Degree of Fixing     67%                                                      Flameproof Character treated   untreated                                      ______________________________________                                        after post-wash: burning time, sec.  Tear length, cm after 5 ×          SNV-198861 washes:  Burning time, sec. Tear length, cm after 10 ×       SNV-198861 washes: Burning time, sec. Tear length, cm after 40×         SNV-198861 washes: Burning time, sec. Tear length, cm                                              0 7  0  3  0  3.5  0  3                                                                  ##STR6##                                      ______________________________________                                    

EXAMPLE 28

A sheepskin and a rabbit fur are each sprayed with the following liquor:590 g/l of the product according to Example 9, 85 g/l ofdimethylolmelamine and 2 g/l of a condensation product of 1 mol ofp-tert.-nonylphenol and 9 mols of ethylene oxide.

The liquor thus contains 67 g/l of phosphorus and 35 g/l of nitrogen.After spraying, the material is dried at 80° C. The deposit after dryingis in each case about 10%.

In the flameproofing test according to DIN 53,906, using an ignitiontime of 4 seconds, the test specimens provided with the finish do notburn, whilst the skins and furs without finish immediately burn through.

EXAMPLE 29

Wooden shingles (fir) 2 mm thick are immersed for 5 or 15 minutes intothe following liquor: 590 g/l of the product according to Example 9, 85g/l of dimethylolmelamine and 2 g/l of a condensation product of 1 molof p-tert.-nonylphenol and 9 mols of ethylene oxide.

The liquor thus contains 67 g/l of phosphorus and 35 g/l of nitrogen.After the liquor has been allowed to drain off, the shingles are driedat 80° C. The deposit is 24 and 30% respectively.

The flameproofing test according to DIN 53,906 gives the followingresults:

    ______________________________________                                                   Time of Immersion                                                             5 minutes                                                                              15 minutes Untreated                                      ______________________________________                                        Burning time, sec. Burning length, cm                                                      10  6      0 5                                                                                       ##STR7##                                  ______________________________________                                    

EXAMPLE 30

Ashless filterpaper (70 g/m²) is padded with the following liquor: 590g/l of the product according to Example 9, 85 g/l of dimethylolmelamineand 2 g/l of a condensation product of 1 mol of p-tert.-nonylphenol and9 mols of ethylene oxide.

The liquor thus contains 67 g/l of phosphorus and 35 g/l of nitrogen.The liquor uptake is 105%. The paper is dried at 80° C. The deposit is55%.

The flameproofing test according to DIN 53,906 shows a burning time of 0seconds and a burning length of 6 cm, whilst untreated filterpaper iscompletely burnt.

We claim:
 1. Process for the flameproofing of organic fibre materials,which comprises applying an aqueous preparation to these materials whichcontains at least1. a polycondensation product of hydroxymethylphosphonium compounds, wherein said product is made by condensing atleast one anhydrous tetrakis-(hydroxymethyl)-phosphonium salt ortetrakis-(hydroxymethyl)-phosphonium hydroxide with itself in ananhydrous medium at 100° to 150° C until 0.5 to 1.5 mols of water havebeen eliminated per 1 mol of hydroxymethylphosphonium starting materialand
 2. an aminoplast precursor or aminoplast precondensate, and that thematerials thus treated are dried and subjected to a heat treatment. 2.Process according to claim 1, which comprises using a methylolurea or amethylolmelamine as component 2).
 3. Process according to claim 1, whichcomprises flameproofing fibre material of polyamides, cellulose,cellulosepolyester or polyester.
 4. Process according to claim 3, whichcomprises flameproofing fabrics of wool or polyester or mixed fabrics ofpolyester-cellulose.
 5. Process according to claim 1, which comprisesdrying the fibre material at temperatures of up to 100° C and subjectingto a heat treatment above 100° C.
 6. The organic fibre materialsprovided with a flameproof finish according to the process of claim 1.